Ultrasound coupled with supercritical carbon dioxide for exfoliation of graphene: Simulation and experiment

Ultrasound coupled with supercritical CO₂ has become an important method for exfoliation of graphene, but behind which a peeling mechanism is unclear. In this work, CFD simulation and experiment were both investigated to elucidate the mechanism and the effects of the process parameters on the exfoliation yield. The experiments and the CFD simulation were conducted under pressure ranging from 8 MPa to 16 MPa, the ultrasonic power ranging from 12 W to 240 W and the frequency of 20 kHz. The numerical analysis of fluid flow patterns and pressure distributions revealed that the fluid shear stress and the periodical pressure fluctuation generated by ultrasound were primary factors in exfoliating graphene. The distribution of the fluid shear stress decided the effective exfoliation area, which, in turn, affected the yield. The effective area increased from 5.339 cm³ to 8.074 cm³ with increasing ultrasonic power from 12 W to 240 W, corresponding to the yield increasing from 5.2% to 21.5%. The pressure fluctuation would cause the expansion of the interlayers of graphite. The degree of the expansion increased with the increase of the operating pressure but decreased beyond 12 MPa. Thus, the maximum yield was obtained at 12 MPa. The cavitation might be generated by ultrasound in supercritical CO₂. But it is too weak to exfoliate graphite into graphene. These results provide a strategy in optimizing and scaling up the ultrasound-assisted supercritical CO₂ technique for producing graphene.     

Preparation and luminescence of (SBA-15)–Eu2O3 composite materials

In this study, (SBA-15)–Eu₂O₃ host-guest composites have been prepared with SBA-15 mesoporous sieve as host and Eu₂O₃ as guest via the solid-phase ultrasonic method and liquid-phase medium ultrasonic method. The host–guest composite materials showed the properties of luminescence. Four excitation peaks appeared in the excitation spectra of the samples. The excitation peaks are located at 397, 415, 466, 537 nm; 392, 408, 464, 532 nm and 393, 406, 465, 533 nm for the nano-Eu₂O₃, the liquid-phase medium ultrasonic method (LPMUM) and the solid-phase ultrasonic method (SPUM) samples, respectively. SBA-15 has the well-ordered hexagonal arrays of mesopores, which makes centrosymmetry of Eu³⁺ higher in the prepared (SBA-15)–Eu₂O₃ samples. The intensity of ⁵D₀→⁷F₁ transition strengthens, and the intensity of ⁵D₀→⁷F₂ transition weakens.     

Preparation of poly(2-ethyl aniline)/kaolinite composite materials and investigation of their properties

Conductive poly(2-ethyl aniline) (PEAn)/kaolinite composite was prepared by chemical polymerization in aqueous HCl medium in the presence of kaolinite particles by using potassium chromate (K₂CrO₄) as oxidant. Effects of polymerization conditions, such as concentrations of oxidant and 2-ethyl aniline, polymerization time and temperature on PEAn content and conductivity of composite, were investigated. The prepared composite material, having the highest PEAn content and conductivity, was obtained in the polymerization carried out at 20 °C for 2 h with 0.2 M K₂CrO₄ and 0.2 M EAn. It was observed that the micro-hardness of prepared composites increased with the increase in the PEAn contents of composites. The highest micro-hardness value of 7.92 kg mm⁻² was reached at 24.6% PEAn content. Characterization of composites was carried out by FTIR spectroscopy, XRD, TGA and SEM techniques.     

Significant positive magnetoresistance of graphene/carbon composite films prepared by electrospraying and subsequent heat treatment

Graphene/carbon composite films were prepared by electrospraying a graphene/polyacrylonitrile composite solution on SiO₂-coated silicon substrates and subsequent heat treatment. The as-produced graphene/carbon composite films had a porous structure comprising graphene layers. With a magnetic field applied perpendicularly to the sample, an unexpectedly significant positive magnetoresistance attributed to e–e interaction and weak localization has been observed, which constantly increases with the magnetic field in the temperature range of 300–50 K from 0 to 80 kOe.     

Water-mediated modulation of TiO2 decorated with graphene for photocatalytic degradation of trichloroethylene

The improvement of photocatalytic properties of TiO₂ was achieved by using water-mediated TiO₂ decorated with graphene (WTiO₂-d-graphene) composites. This work describes the photocatalytic degradation of trichloroethylene (TCE) in the presence of WTiO₂-d-graphene composites. WTiO₂-d-graphene composite photocatalysts, containing different amounts of graphene, were prepared by facile ultrasonic assisted techniques and thermal reaction. The surface properties of these WTiO₂-d-graphene composites were characterized by X-ray photoelectron spectroscopy (XPS). Peaks attributable to C–C (284.4 eV), denoted as the C_1s spectrum, and C–O bonds (288.6 eV) appeared simultaneously in the XPS spectrum. It was inferred that this was due to the presence of Ti–O–C bonds. The photocatalytic properties were determined by monitoring the degradation of TCE in the headspace of the vial at different times using gas chromatography. From the results, it was apparent that the photocatalytic activities of WTiO₂-d-graphene composites were higher than that of pure TiO_2. This can be attributed to their ability to absorb light over a wider range of wavelengths.     

Preparation of Aromatic Polycarbonate Nanoparticles using Supercritical Carbon Dioxide

A novel synthetic process for producing aromatic polycarbonate (PC) nanoparticles using supercritical CO₂ was developed. The objective of the present research work was to synthesize high molecular weight PC nanoparticles using transesterification between bisphenol-A (BPA) and diphenyl carbonate (DPC) in supercritical CO₂ which is an excellent plasticizing agent and a good solvent for phenol, a by-product of the reaction. Poly(propylene oxide)–poly(ethylene oxide)–poly(propylene oxide) tri-block copolymer with CO₂-phobic anchor and CO₂-philic tail group was used as a stabilizer for the preparation of stable dispersions of BPA–DPC mixture in a CO₂ continuous phase. As the reaction was proceeding, phenol formed from the reaction was dissolved and diffused into supercritical CO₂ phase. The PC nanoparticles were isolated by simple venting of the supercritical CO₂ from the reactor. Spherical morphology of PC particles was confirmed by scanning electron microscopy. Particle size and morphology of PC particles were modified upon variation of the process conditions. The resulting PC particles with a nano-size of 30–140nm have a high molecular weight (M _w) of 3.1×10⁵ (g/mol).     

Structural,morphological and magnetic characterization of synthesized Co-Ce doped Ni ferrite /Graphene /BNO12 nanocomposites for practical applications

Cobalt-cerium (Co-Ce) doped nickel ferrite (F) nanoparticles having formula Ni_0.8Ce_0.2Co_0.5Fe_1.5O₄ were prepared by the sol-gel auto combustion method. Graphene coated Co-Ce doped Ni ferrite (F/G) and polymer (Lugalvan BNO12) coated F/G ternary nanocomposites (F/G/P) were prepared by the dispersion method. Different characterization techniques were used to investigate the different properties of these synthesized samples. TG-DTA showed the thermal degradation of all composites up to 900 C. The FTIR spectra revealed the presence of two absorption bands that confirmed the ferrite contents in all three composites. It also showed the aromatic contents in the F/G and F/G/P composites due to the presence of graphene and polymer. The XRD patterns revealed a single phase of Ni ferrite doped with Co-Ce without other intermediate phases. The crystallite size was found to be 32.41 nm maximum for the F/G/P composites. The SEM images showed that the surface of the F/G nanocomposite was uniformly coated by Lugalvan BNO12 polymer molecular chains. EDX confirmed the presence of the respective components in all prepared composites. VSM characterization was used to measure the hysteresis loops for the determination of the anisotropy constant, magnetic moments, initial permeability, squareness ratio, remanence and saturation magnetization. These parameters showed a decrease in values in the following order F/G/P > F/G > F. F/G/P revealed the highest coercivity (279.2 G). The fascinating magnetic activity of this nanocomposite makes it a potential candidate in the applications of energy storage, adsorbents for pollutants remediation technologies, electrochemical sensors, chemical process catalysts and electromagnetic wave absorbers.     

Composites of olive-like manganese oxalate on graphene sheets for supercapacitor electrodes

MnC₂O₄/graphene composites are prepared by a facile hydrothermal reaction with KMnO₄ using ascorbic acid as a reducing agent. Olive-like MnC₂O₄ particles are distributed uniformly on the surface of graphene sheets. The composites are evaluated as supercapacitor electrodes, which show that the specific capacitance of MnC₂O₄/graphene composites is 122 F g^?1, more than twice as high as that of free MnC₂O₄ at a current density of 0.5 A g^?1. In addition, this composite material exhibits an excellent cycle stability with the capacitance retention of 94.3 % after 1,000 cycles.     

Preparation of Silica/Poly(divinylbenzene) Composite Particles by Dispersion Polymerization in Supercritical Carbon Dioxide

Silica/poly(divinylbenzene) (PDVB) composite particles were synthesized by the dispersion polymerization of divinylbenzene (DVB) with ultrafine silica particles in supercritical carbon dioxide (scCO₂). Silica particles of average diameter 130 nm were pretreated with 3-(trimethoxysilyl) propyl methacrylate in order to be well dispersed in CO₂ and participated in the polymerization. Random copolymeric dispersant, poly(diisopropylaminoethyl methacrylate-co-heptafluorobutyl methacrylate) was used as a stabilizer to provide sufficient stabilization to latexes in scCO₂ and the silica/PDVB composite powder was obtained in high yield from the polymerization. SEM analysis revealed that the composite particles prepared at 5% silica loading ratio and 6% stabilizer concentration with respect to monomer have the average diameter of 1.60 μm with uniform and spherical morphology. The composites were also characterized by FTIR spectroscopy and TGA.     

Preparation of Co3O4 nanoplate/graphene sheet composites and their synergistic electrochemical performance

Co₃O₄ nanoplate/graphene sheet composites were prepared through a two-step synthetic method. The composite material as prepared was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The platelet-like morphology of Co₃O₄ leads to a layer-by-layer-assembled structure of the composites and a good dispersion of Co₃O₄ nanoplates on the surface of graphene sheets. The electrochemical characteristics indicate that the specific capacitance of the composites is 337.8 F?g^?1 in comparison with the specific capacitance of 204.4 F?g^?1 without graphene sheets. Meanwhile, the composites have an excellent rate capability and cycle performance. The results show that the unique microstructure of the composites enhances the electrochemical capacitive performance of Co₃O₄ nanoplates due to the three-dimensional network of graphene sheets for electron transport increasing electric conductivity of the electrode and providing unobstructed pathways for ionic transport during the electrochemical reaction.     

The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

Microwave-assisted rapid synthesis of Ag nanoparticles/graphene nanosheet composites and their application for hydrogen peroxide detection

Abstract  

Ag nanoparticles/graphene nanosheet (AgNPs/GN) composites have been rapidly prepared by a one-pot microwave-assisted reduction method, carried out by microwave irradiation of a N,N-dimethylformamide (DMF) solution of graphene oxide (GO) and AgNO₃. Several analytical techniques including UV–vis spectroscopy, FT-IR spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) have been used to characterize the resulting AgNPs/GN composites. It suggests that such composites exhibit good catalytic activity toward reduction of hydrogen peroxide (H₂O₂), leading to a H₂O₂ sensor with a fast amperometric response time of less than 2 s. The linear detection range is estimated to be from 0.1 to 100 mM (r = 0.999), and the detection limit is estimated to be 0.5 μM at a signal-to-noise ratio of 3.     

Low intensity-ultrasonic irradiation for highly efficient,eco-friendly and fast synthesis of graphene oxide

High quality graphene oxide (GO) with low layer number (less than five layers) and large inter-layer space was produced via a new and efficient method using environmentally friendly, fast and economic ultrasonic radiation. The ultrasonic method neither generated any toxic gas nor required any NaNO₃, which have been the main drawbacks of the Hummers methods. The major obstacles of the recently reported improved Hummers method for GO synthesis, such as high reaction temperature (50 °C) and long reaction time (12 h), were successfully solved using a low intensity-ultrasonic bath for 45 min at 30 °C, which significantly reduced the reaction time and energy consumption for GO synthesis. Furthermore, ultrasonic GO exhibited higher surface area, higher crystallinity and higher oxidation efficiency with many hydrophilic groups, fewer sheets with higher spaces between them, a higher sp³/sp² ratio, and more uniform size distribution than classically prepared GO. Therefore, the new ultrasonic method could be applicable for the sustainable and large-scale production of GO. The production yield of the ultrasonic-assisted GO was 1.25-fold greater than the GO synthesized with the improved Hummers method. Furthermore, the required production cost based on total energy consumption for ultrasonic GO was only 6.5% of that for classical GO.     

Ultrasonic-assisted electrodeposition of Ni/diamond composite coatings and its structure and electrochemical properties

Ni/diamond composite coatings have been synthesized by ultrasonic-assisted electrodeposition in a Ni electroplating bath containing diamond nanoparticles. The influences of current density and ultrasonic agitation on the coating composition, morphology, topography, phase structure, and electrochemical characteristics of the electrodeposits were evaluated. Ultrasonic agitation was provided using an external ultrasonic bath at a frequency of 40 kHz and acoustic power of 300 W. Coating samples were also prepared under magnetic stirring for comparison with the ultrasonic-assisted deposits. This work reveals that the diamonds have been incorporated and evenly distributed in the composites. The coatings exhibit dense, granular like morphology with pyramid-like grains. As current density increases, the diamond amount of ultrasonic-assisted electrodeposits first increased to maximum of 11.4 wt% at 3 A dm⁻² and then decreases to 9.9 wt% at 5 A dm⁻², and the RTC of the preferred orientation (2 0 0) plane increases from 76.3% up to 93.4%. The crystallite size was 60–80 nm and the R_a of the magnetic and ultrasonic agitations were 116 nm, 110 nm, respectively. The maximum R_p of 39.9, 50.3 kΩ cm² was obtained at 4 A dm⁻² when respectively immersed 30 min and 7 days, illustrating the best corrosion resistance of the coatings of 4 A dm⁻². The effects of mechanical and ultrasonic agitations on the mechanism of the co-electrodeposition process were both proposed. The incorporation of diamond particles enhances the hardness and wear-resisting property of the electrodeposits. The ultrasonic-assisted electrodeposited Ni/diamond coating has better corrosion resistance than that prepared under mechanical stirring conditions.     

Luminescence of CdS:Ag Quantum Dots in a Polymethacrylate Matrix

Semiconductor quantum dots (QDs) exhibit intense luminescence and reproduce optical characteristics. Doping with metal ions has a positive effect on their properties. Introduction of QDs into polymer matrices leads to the formation of a required morphology of composites. There is a problem in synthesis of optically transparent polymer composites containing QDs of the А²В⁶ group that consists in the extremely low solubility of metal chalcogenides and most of their precursors in monomers. To solve this problem, we used colloidal synthesis. CdS QDs were synthesized by the method of appearing reagents in situ in methylmethacrylate (MMA). Doping with Ag⁺ ions was performed by adding a silver salt into the reaction mixture during the synthesis of CdS QDs. The PMMA/CdS:Ag luminescent polymer glasses were synthesized by radical block polymerization of MMA. The transparency of the composites at wavelengths exceeding 500 nm reaches 92% (5 mm). The luminescence excitation is related to the interband electron transitions in CdS crystals. Luminescence in the range of 500–600 nm is observed due to electron relaxation via a system of levels in the band gap of doped CdS crystals. The positions and intensities of the spectral bands depend on the Ag⁺ concentration, particle size, excitation wavelength, and other factors. The formation of Cd(Ag)S/Ag₂S structures at Ag⁺ concentrations higher than 5.0 × 10^–3 mol/L quenches the luminescence.     

Analytical calculations and properties of γ-rays polymerization of novel acrylates copolymer system

A detailed study of some physical properties of pure PMMA (polymethyl methacrylate) film and MMA/Ani (methyl methacrylate/aniline) films is presented. Films of thicknesses ranged from 0.04 to 0.72 mm for MMA/Ani were prepared while it is 0.68 mm for PMMA. The structure of the sample is analyzed by X-ray diffraction technique and is found to be amorphous (PMMA) and partially crystalline (MMA/Ani). Ultra violet–visible electronic absorption spectra measurements were analyzed to obtain some important parameters such as molar extrication coefficient, oscillator strength, dipole strength and having good thermal stability (T_d >300 °C) was also reported. TGA studies revealed that the thermal stability of polymethyl methacrylate, prepared by radiation polymerization of methyl methacrylate, improved after copolymerization with aniline. Also, optical behavior of film samples was analyzed by obtaining transmission spectra, in the wavelength range of 200–1100 nm. It was found that all studied samples lead to the appearance of a second edge at lower photon energy due to the formation of the induced energy states. From the intensity of absorption interband transitions (B and Q) which are assigned as type π–π^* for both PMMA and MMA/Ani films, the energy gaps E_g1 and E_g2 were calculated respectively. The optical conductivity (σ) was determined and it was found that with the increase of thicknesses optical energy gap decreases monotonically and the refractive index increases.     

Ultrasonic assisted synthesis of Ni3(VO4)2-reduced graphene oxide nanocomposite for potential use in electrochemical energy storage

In the present study, Ni₃(VO₄)₂-reduced graphene oxide (NV/RGO) nanocomposite was synthesized for energy storage purpose. To this end, a mixture containing RGO nanosheets, Ni (CH₃COOH)₂ and Na₃VO₄ mixture was prepared under probe-type ultrasonic irradiation with frequency of 20 KHz and the optimized power of 100 W. The Raman and energy-dispersive X-ray spectroscopies confirmed the presence of RGO nanosheets, nickel and vanadium elements in the NV/RGO, respectively. In addition, field emission-scanning electron microscopy (FESEM) data showed the formation of the NV nanoparticles on the RGO nanosheets. NV/RGO nanocomposite was pasted on nickel foam (NF) and its performance was investigated in energy storage using a three-electrode cell containing 6 M KOH. In cyclic voltammogram of NV/RGO/NF, redox peaks for Ni (II)/Ni (III) with intensities higher than that for NV/NF were observed which confirms the synergistic effect of RGO on the performance of NV. Chronopotentiometry data revealed that the NV/RGO/NF electrode exhibits high capacity of 117.22 mA h g⁻¹ at 2 A g⁻¹. Electrochemical impedance spectroscopy also demonstrated an improvement in the electrical conductivity and electrochemical behavior of NV/RGO/NF nanocomposite compared to the RGO/NF and NV/NF. Furthermore, NV/RGO/NF electrode reserved about 88% of its initial capacity after 1000th potential cycle at 50 mV s⁻¹. Overall, the results of our study suggest that the NV/RGO nanocomposite prepared in the presence of ultrasonic irradiation might be regarded as a suitable active material for energy storage systems.     

Preparation of binder-free thin film Li4Ti5O12 anode with an adjustable thickness through anodic TiO2 nanotubes

Binder-free thickness-controllable Li₄Ti₅O₁₂ for application in lithium ion batteries was fabricated by the reaction of Li₂CO₃ and anodic nanotubular TiO₂ at 800 °C. As the concentration of Li₂CO₃ increased, the thickness of Li₄Ti₅O₁₂ film increased, leading to increase in discharge capacity. The Li₄Ti₅O₁₂ film prepared at the optimized concentration of Li₂CO₃ of 3.8 × 10^?6 mol displayed the maximum capacity of 104 μA h cm^?2 at the first cycle, which corresponds to 103 mA h g^?1. We found that excess Li₂CO₃ led to creation of LiTiO₂ phases in the Li₄Ti₅O₁₂ film, which reduced the discharge capacity. For comparison, a Li₄Ti₅O₁₂ film was prepared by the reaction of Li₂CO₃ on a non-anodized Ti foil. In this case, discharge capacity was dramatically reduced due to the formation of Li₂TiO₃ phases in Li₄Ti₅O₁₂, which was confirmed by TEM and XRD analysis.     

Ultrasonically assisted synthesis of barium stannate incorporated graphitic carbon nitride nanocomposite and its analytical performance in electrochemical sensing of 4-nitrophenol

We describe the ultrasonic assisted preparation of barium stannate-graphitic carbon nitride nanocomposite (BSO-gCN) by a simple method and its application in electrochemical detection of 4-nitrophenol via electro-oxidation. A bath type ultrasonic cleaner with ultrasonic power and ultrasonic frequency of 100 W and 50 Hz, respectively, was used for the synthesis of BSO-gCN nanocomposite material. The prepared BSO-gCN nanocomposite was characterized by employing several spectroscopic and microscopic techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, fourier transform infra-red, field emission scanning electron microscopy, and high resolution transmission electron microscopy, to unravel the structural and electronic features of the prepared nanocomposite. The BSO-gCN was drop-casted on a pre-treated glassy carbon electrode (GCE), and their sensor electrode was utilized for electrochemical sensing of 4-nitrophenol (4-NP). The BSO-gCN modified GCE exhibited better electrochemical sensing behavior than the bare GCE and other investigated electrodes. The electroanalytical parameters such as charge transfer coefficient (α = 0.5), the rate constant for electron transfer (k_s = 1.16 s⁻¹) and number of electron transferred were calculated. Linear sweep voltammetry (LSV) exhibited increase in peak current linearly with 4-NP concentration in the range between 1.6 and 50 μM. The lowest detection limit (LoD) was calculated to be 1 μM and sensitivity of 0.81 μA μM⁻¹ cm⁻²_. A 100-fold excess of various ions, such as Ca²⁺, Na⁺, K⁺, Cl⁻, I⁻, CO₃²⁻, NO₃, NH₄⁺ and SO₄²⁻ did not able to interfere with the determination of 4-NP and high sensitivity for detecting 4-NP in real samples was achieved. This newly developed BSO-gCN could be a potential candidate for electrochemical sensor applications.     

Influences of compositions and ligands on photoluminescent properties of Eu(III) ions in composite europium complex/PMMA systems

Three kinds of europium complexes; Eu(phen)₂Cl₃(H₂O)₂, Eu(DN-bpy)phenCl₃(H₂O)₂ and Eu(DB-bpy)phenCl₃(H₂O)₂ (phen: 1,10-phenanthroline, DN-bpy: 4,4′-Dinonyl-2,2′-dipyridyl, DB-bpy: 4,4′-Di-tert-butyl-2,2′-dipyridyl) were prepared and then incorporated into polymethyl methacrylate (PMMA) matrix with different molar ratios of CO groups/Eu³⁺ ions. The final solid composites were formed by a self-assembly process among Eu³⁺ ion, the ligands and PMMA during the solvent evaporation process, and then the ligands re-coordinate to Eu(III). It was found that the ligands affect not only the emission properties of the pure complexes, but also the miscibility of the complexes and PMMA. More than one kind of symmetric sites of Eu³⁺ ions were formed in the composites due to the coordination of CO in PMMA to Eu³⁺ ions. The micro-environments of Eu(III) in the composites were changed with the compositions and the ligands, leading to the change in the crystalline structure, and consequently, the emission characteristics.